Fungicidal hydroxyalkyl-triazolyl derivatives

ABSTRACT

Fungicidal hydroxyalkyl-triazdyl derivatives of the formula ##STR1## in which R represents a radical of the formula --CH 2  --CH(CH 3 ) 2 , --(CH 2 ) 4  --CH 3 , --(CH 2 ) 5  --CH 3 , --(CH 2 ) 6  --CH 3 , ##STR2## Z represents halogen, alkyl with 1 to 4 carbon atoms, halogenoalkyl with 1 or 2 carbon atoms and 1 to 5 halogen atoms, halogenoalkoxy with 1 or 2 carbon atoms and 1 to 5 halogen atoms, halogenoalkylthio with 1 or 2 carbon atoms and 1 to 5 halogen atoms, phenyl or alkoximinimethyl with 1 to 4 carbon atoms in the alkoxy group and 
     m represents the numbers 0, 1, 2 or 3, 
     and addition products thereof with acids and metal salts. Intermediates of the formulas ##STR3## are also new.

This is a division of application Ser. No. 190,733, filed May 5, 1988,now U.S. Pat. No. 4,894,383.

The present invention relates to new hydroxyalkyltriazolyl derivatives,a process for their preparation and their use as fungicides.

It has already been disclosed that numerous hydroxyalkyl-azolylderivatives possess fungicidal properties (compare EP-OS (EuropeanPublished Specification) No. 0,040,345 and EP-OS (European PublishedSpecification) No. 0,061,835). Thus1-(4-chlorophenyl)-4,4-dimethyl-3-(1,2,4-triazol-1-yl-methyl)pentan-3-ol,for example, is employed for combating fungi. The activity of thissubstance is very good; however, the plant tolerability and the activityin some cases leaves something to be desired.

New hydroxyalkyl-triazolyl derivatives of the formula ##STR4## in whichR represents the radicals of the formulae --CH₂ --CH(CH₃)₂ --(CH₂)₄--CH₃, --(CH₂)₅ --CH₃, --(CH₂)₆ --CH₃, ##STR5## Z represents halogen,alkyl with 1 to 4 carbon atoms, halogenoalkyl with 1 or 2 carbon atomsand 1 to 5 halogen atoms, halogenoalkoxy with 1 or 2 carbon atoms and 1to 5 halogen atoms, halogenoalkylthio with 1 or 2 carbon atoms and 1 to5 halogen atoms, phenyl or alkoximinomethyl with 1 to 4 carbon atoms inthe alkoxy group and

m represents the numbers 0, 1, 2 or 3,

and their acid addition salts and metal salt complexes, have been found.

The new hydroxyalkyl-triazolyl derivatives of the formula (I) possess anasymmetrically substituted carbon atom and can therefore exist in twooptical isomeric forms. The invention relates both to the racemates andto the separate isomers and their mixtures.

Furthermore, it has been found that hydroxyalkyltriazolyl derivatives ofthe formula (I) and their acid addition salts and metal salt complexesare obtained when oxiranes of the formula ##STR6## in which R, Z and mhave the abovementioned meaning, are reacted with 1,2,4-triazole of theformula ##STR7## in the presence of a diluent and if appropriate in thepresence of an acid binding agent and if appropriate in the presence ofa catalyst and then if appropriate an acid or a metal salt issubsequently adducted to the compounds of the formula (I) so obtained.

Finally it has been found that the hydroxyalkyltriazolyl derivatives ofthe formula (I) and their acid addition salts and metal salt complexesare distinguished by very good fungicidal properties.

Surprisingly, the substances according to the invention possess a betterfungicidal activity than1-(4-chlorophenyl)-4,4-dimethyl-3-(1,2,4-triazol-1-yl-methyl)-pentan-3-ol,which is a constitutionally similar, previously known active substancewith an equivalent type of action. In addition the substances accordingto the invention exhibit outstanding plant tolerability.

Formula (I) provides a general definition of the hydroxyalkyl-triazolylderivatives according to the invention. Preferred compounds of theformula (I) are those in which

R represents the radicals of the formulae --CH₂ --CH(CH₃)₂, --(CH₂)₄--CH₃, --(CH₂)₅ --CH₃, --(CH₂)₆ --CH₃, ##STR8## Z represents fluorine,chlorine, bromine, methyl, ethyl, trifluoromethyl, trifluoromethoxy,trifluoromethylthio, phenyl, methoximinomethyl or ethoximinomethyl and

m represents the numbers 0, 1, 2 or 3.

When m represents 2 or 3, the substituents for Z can be identical ordifferent.

Addition products of acids and those hydroxyalkyltriazolyl derivativesof the formula (I), in which R, Z and m have those meanings which havealready been mentioned as preferred for these substituents or this indexin connection with the description of the substances according to theinvention are also preferred compounds according to the invention.

The acids which can be added preferably include hydrohalic acids, suchas, for example, hydrochloric acid and hydrobromic acid, in particularhydrochloric acid, furthermore to phosphoric acid, nitric acid, mono-and bi-functional carboxylic acids and hydroxycarboxylic acids, such as,for example, acetic acid, maleic acid, succinic acid, fumaric acid,tartaric acid, citric acid, salicylic acid, sorbic acid and lactic acid,and sulphonic acids, such as, for example, p-toluenesulphonic acid and1,5-naphthalenedisulphonic acid.

Addition products of salts of metals of the main groups II to IV and thesubgroups I and II and also IV to VIII of the periodic table of theelements and those hydroxyalkyl-triazolyl derivatives of the formula(I), in which R, Z and m have those meanings which have already beenmentioned as preferred for these substituents or this index inconnection with the description of the substances according to theinvention are additionally preferred compounds according to theinvention.

Herein, salts of copper, zinc, manganese, magnesium, tin, iron andnickel are particularly preferred. Possible anions of these salts arethose which are derived from acids which lead to addition products whichare physiologically tolerable for plants. In this connection,particularly preferred acids of this type are the hydrohalic acids, suchas, for example, hydrochloric acid and hydrobromic acid, furthermorephosphoric acid, nitric acid and sulphuric acid.

Examples which may be mentioned for the compounds according to theinvention are the substances shown in the following table.

                  TABLE                                                           ______________________________________                                         ##STR9##                      (I)                                            Z.sub.m        R                                                              ______________________________________                                        2,4-Cl.sub.2   (CH.sub.2).sub.4CH.sub.3                                       4-F            "                                                              4-CHNOCH.sub.3 "                                                              2,6-Cl.sub.2   "                                                               ##STR10##     "                                                              --             "                                                              4-CF.sub.3     "                                                              4-CH.sub.3     "                                                              2,4-Cl.sub.2   (CH.sub.2).sub.5CH.sub.3                                       4-F            "                                                              4-CHNOCH.sub.3 "                                                              2,6-Cl.sub.2   "                                                               ##STR11##     "                                                              --             "                                                              4-CF.sub.3     "                                                              4-CH.sub.3     "                                                              2,4-Cl.sub.2   (CH.sub.2).sub.6CH.sub.3                                       4-F            "                                                              4-CHNOCH.sub.3 "                                                              2,6-Cl.sub.2   "                                                               ##STR12##     "                                                              --             "                                                              4-CF.sub.3     "                                                              4-CH.sub.3     "                                                              2,4-Cl.sub.2                                                                                  ##STR13##                                                     4-F            "                                                              4-CHNOCH.sub.3 "                                                              2,6-Cl.sub.2   "                                                               ##STR14##     "                                                              --             "                                                              4-CF.sub.3     "                                                              4-CH.sub.3     "                                                              2,4-Cl.sub.2                                                                                  ##STR15##                                                     4-F            "                                                              4-CHNOCH.sub.3 "                                                              2,6-Cl.sub.2   "                                                               ##STR16##     "                                                              --             "                                                              4-CF.sub.3     "                                                              4-CH.sub.3     "                                                              ______________________________________                                    

If 2-[2-(4-chlorophenyl)-ethyl]-2-[(1,1-dimethyl)butyl]-oxirane and1,2,4-triazole are used as starting substances, then the course of theprocess according to invention can be represented by the followingequation: ##STR17##

Formula (II) provides a general definition of the oxiranes to be used asstarting substances in carrying out the process according to theinvention. In this formula, R, Z and the index m preferably have thosemeanings which have already been mentioned as preferred for thesesubstituents or for the index m in connection with the description ofthe substances of the formula (I) according to the invention.

The oxiranes of the formula (II) were hitherto unknown. They can beprepared by a process in which

(a) in a first step, ketones of the formula ##STR18## in which R, Z andm have the abovementioned meaning, are reacted withmethyl-triphenyl-phosphonium bromide of the formula ##STR19## in thepresence of a base and in the presence of a diluent and then in a secondstep the compounds so obtained of the formula ##STR20## in which R, Zand m have the abovementioned meaning, with peracids in the presence ofa diluent, or

(b) ketones of the formula ##STR21## in which R, Z and m have theabovementioned meaning, are reacted either

(α) with dimethyloxosulphonium methylide of the formula ##STR22## or (β)with dimethylsulphonium methylide of the formula ##STR23## in thepresence of a diluent.

The ketones of the formula (IV) required as starting substances in thepreparation of the oxiranes of the formula (II) are known or can beprepared in a simple manner by processes which are known in principle(compare EP-OS (European Published Specification) No. 0,084,834). Thusketones of the formula (IV) are obtained by reacting compounds of theformula ##STR24## in which R' has the abovementioned meaning for R orrepresents corresponding unsaturated counterparts of R,

with aldehydes of the formula ##STR25## in which Z and m have theabovementioned meaning, in the presence of a diluent, such as, forexample, ethanol, at temperatures between 0° and 60° C. andhydrogenating the compounds of the formula ##STR26## in which R', Z andm have the abovementioned meaning, resulting in this reaction, usinghydrogen in the presence of a catalyst, such as, for example, Raneynickel, in the presence of a diluent, such as, for example, toluene ortetrahydrofuran, at temperatures between 40° and 180° C. (compare thepreparation examples).

The compounds of the formula (IX) and also the aldehydes of the formula(X) are known or can be prepared in a simple manner by known processes.

The methyl-triphenyl-phosphonium bromide of the formula (V) furthermorerequired as starting material in the preparation of the oxiranes of theformula (II) according to process (a) is known.

The compounds of the formula (VI) required in the second step asstarting substances in the preparation of the oxiranes of the formula(II) according to the above process (a) were hitherto unknown.

In process (a) for the preparation of the oxiranes of the formula (II),the first step is carried out in the presence of a base. Possible baseshere are all bases conventionally utilizable for Wittig reactions ofthis type. Potassium tert.-butylate is preferably utilizable.

In carrying out the first step of the above process (a) for thepreparation of the oxiranes of the formula (II), suitable diluents areall organic solvents customary for such reactions. Aromatichydrocarbons, such as benzene, toluene and xylene, are preferablyutilizable.

In carrying out the second step of the above process (a) for thepreparation of the oxiranes of the formula (II), possible reagents forepoxidation are all the customary peracids. Meta-chloroperbenzoic acidand peracetic acid are preferably utilizable. In addition, it is alsopossible to employ a mixture of acetic acid and hydrogen peroxide.

In carrying out the second step of the above process (a) for thepreparation of the oxiranes of the formula (II), suitable diluents areall the solvents customary for such epoxidations. Dichloromethane,chloroform, toluene, dichlorobenzene, acetic acid and other inertsolvents are preferably utilizable.

In carrying out process (a) for the preparation of the oxiranes of theformula (II), the reaction temperatures can be varied within a certainrange. In general the first step is carried out at temperatures between50° C. and 140° C., preferably between 80° C. and 120° C. The secondstep is generally carried out between 10° C. and 60° C., preferablybetween 20° C. and 50° C.

In carrying out the process (a) for the preparation of the oxiranes ofthe formula (II), a procedure is generally followed in which between 1and 3 mols of methyltriphenylphosphonium bromide of the formula (V) andbetween 1 and 3 mols of base are employed per mol of ketone of theformula (IV) in the first step. In the second step, between 1 and 2 molsof peracid are in each case employed per mol of a compound of theformula (VI). In each case, working up is according to customarymethods.

The dimethyloxosulphonium methylide of the formula (VII) required asreaction component in process (b) is known (compare J. Amer. Chem. Soc.87, 1363-1364 (1965)). It is used in the above reaction in the freshlyprepared state, in that it is obtained in situ by reaction oftrimethyloxo-sulphonium iodide with sodium hydride or sodium amide, inparticular with potassium tert.-butylate or sodium methylate, in thepresence of a diluent.

The dimethylsulphonium methylide of the formula (VIII) additionallypossible as a reaction component in process (b) is also known (compareHeterocycles 8, 397 (1977)). It is also employed in a freshly preparedstate in the above reaction, in that it is obtained in situ, forexample, from trimethylsulphonium halide or trimethylsulphonium methylsulphate, in the presence of a strong base, such as, for example, sodiumhydride, sodium amide, sodium methylate, potassium tert.-butylate orpotassium hydroxide, in the presence of a diluent, such as tert.-butanolor dimethyl sulphoxide.

In carrying out process (b), suitable diluents are inert organicsolvents. Alcohols, such as tert.-butanol, ethers, such astetrahydrofuran or dioxane, furthermore aliphatic and aromatichydrocarbons, such as benzene, toluene or xylene, and also stronglypolar solvents, such as dimethyl sulphoxide, are preferably utilizable.

The reaction temperatures can be varied within a relatively wide rangein process (b). In general, the reaction is carried out at temperaturesbetween 0° and 100° C., preferably between 10° and 60° C.

In carrying out process (b), 1 to 3 mols of dimethyloxosulphoniummethylide of the formula (VII) or dimethylsulphonium methylide of theformula (VIII) are preferably employed per mol of ketone of the formula(IV). The isolation of the oxiranes is according to customary methods.

In the process according to the invention, the oxiranes of the formula(II) can, if appropriate, be directly reacted further without isolation.

Suitable diluents for the process according to the invention are organicsolvents which are inert under the reaction conditions. Alcohols, suchas, for example, ethanol, methoxyethanol or propanol; ketones, such as,for example, 2-butanone and n-methylpyrrolidone; nitriles, such as, forexample, acetonitrile; esters, such as, for example, ethyl acetate;ethers, such as, for example, dioxane; aromatic hydrocarbons, such as,for example, benzene and toluene; or amides, such as, for example,dimethylformamide, are preferably utilizable.

Possible bases for the process according to the invention are all theconventionally utilizable inorganic and organic bases. Alkali metalcarbonates, such as, for example, sodium carbonate and potassiumcarbonate; alkali metal hydroxides, such as, for example, sodiumhydroxide; alkali metal alcoholates, such as, for example, sodiummethylate and potassium methylate, and sodium ethylate and potassiumethylate; alkali metal hydrides, such as, for example, sodium hydride;and also lower tertiary alkylamines, cycloalkylamines and aralkylamines,such as triethylamine in particular, are preferably utilizable.

In carrying out the process according to the invention, suitablecatalysts are all the reaction accelerators conventionally employablefor such reactions. α,α'-Azo-isobutyronitrile is preferably utilizable.

In carrying out the process according to the invention, the reactiontemperatures can be varied within a relatively wide range. In general,the reaction is carried out at temperatures between 0° and 200° C.,preferably between 60° and 150° C.

In carrying out the process according to the invention, the reaction isgenerally carried out under atmospheric pressure. However, it is alsopossible to work under increased or reduced pressure.

In carrying out the process according to the invention, 1 to 2 mols of1,2,4-triazole and, if appropriate, 1 to 2 mols of an acid binding agentare preferably employed per mol of oxirane of the formula (II). Workingup and isolation of the final products are according to customarymethods.

The compounds of the formula (I) obtainable by the processes accordingto the invention can be converted into acid addition salts or metal saltcomplexes.

Suitable acids for the preparation of acid addition salts of thecompounds of the formula (I) are preferably those acids which havealready been mentioned as preferred acids in connection with thedescription of the acid addition salts according to the invention.

The acid addition salts of the compounds of the formula (I) can beobtained in a simple manner by customary salt formation methods, forexample by dissolving a compound of the general formula (I) in asuitable inert solvent and adding the acid, for example, hydrochloricacid, and can be isolated in a known manner, for example by filteringoff, and purified, if necessary, by washing with an inert organicsolvent.

For the preparation of metal salt complexes of the compounds of thegeneral formula (I), suitable salts of metals are preferably those whichhave already been described above.

The metal salt complexes of compounds of the general formula (I) can beobtained in a simple manner by customary processes, for example, bydissolving the metal salt in alcohol, for example ethanol, and adding tocompounds of the general formula (I). Metal salt complexes can beisolated in a known manner, for example by filtering off, and purified,if necessary, by recrystallization.

The active compounds according to the invention exhibit a strongmicrobicidal action and can be employed as fungicides.

Fungicidal agents in plant protection are employed for combatingPlasmodiophoromycetes, Oomycetes, Chytridiomycetes, Zygomycetes,Ascomycetes, Basidiomycetes and Deuteromycetes.

Some causative organisms of fungal and bacterial diseases which comeunder the generic names listed above may be mentioned as examples, butnot by way of limitation: Xanthomonas species, such as Xanthomonasoryzae; Pseudomonas species, such as Pseudomonas lachrymans; Erwiniaspecies, such as Erwinia amylovora; Pythium species, such as Pythiumultimum; Phytophthora species, such as Phytophthora infestans;Pseudoperonospora species, such as Pseudoperonospora humuli orPseudoperonospora cubense; Plasmopara species, such as Plasmoparaviticola; Peronospora species, such as Peronospora pisi or P. brassicae;Erysiphe species, such as Erysiphe graminis; Sphaerotheca species, suchas Sphaerotheca fuliginea; Podosphaera species, such as Podosphaeraleucotricha; Venturia species, such as Venturia inaequalis; Pyrenophoraspecies, such as Pyrenophora teres or P. graminea (conidia form:Drechslera, syn: Helminthosporium); Cochliobolus species, such asCochliobolus sativus (conidia form: Drechslera, syn: Helminthosporium);Uromyces species, such as Uromyces appendiculatus; Puccinia species,such as Puccinia recondita; Tilletia species, such as Tilletia caries;Ustilago species, such as Ustilago nuda or Ustilago avenae; Pelliculariaspecies, such as Pellicularia sasakii; Pyricularia species, such asPyricularia oryzae; Fusarium species, such as Fusarium culmorum;Botrytis species, such as Botrytis cinerea; Septoria species, such asSeptoria nodorum; Leptosphaeria species, such as Leptosphaeria nodorum;Cercospora species, such as Cercospora canescens; Alternaria species,such as Alternaria brassicae and Pseudocercosporella species, such asPseudocercosporella herpotrichoides.

The good toleration, by plants, of the active compounds, at theconcentrations required for combating plant diseases, permits treatmentof above-ground parts of plants, of vegetative propagation stock andseeds, and of the soil.

The substances according to the invention can be employed withparticularly good effect as plant protection agents for combatingVenturia (apple), Cercospora (mungo bean) and also Erysiphe, Puccinia,Leptosphaeria, Cochliobolus and Pyrenophora in cereals and Pyriculariaand Pellicularia in rice.

Moreover, the compounds according to the invention possess a good, widespectrum of action in vitro.

The active compounds can be converted into the customary formulations,such as solutions, emulsions, suspensions, powders, foams, pastes,granules, aerosols, very fine capsules in polymeric substances and incoating compositions for seed, as well as ULV formulations.

These formulations are produced in a known manner, for example by mixingthe active compounds with extenders, that is, liquid solvents, liquefiedgases under pressure, and/or solid carriers, optionally with the use ofsurface-active agents, that is, emulsifying agents and/or dispersingagents, and/or foam-forming agents. In the case of the use of water asan extender, organic solvents can, for example, also be used asauxiliary solvents. As liquid solvents, there are suitable in the main:aromatics, such as xylene, toluene or alkyl naphthalenes, chlorinatedaromatics or chlorinated aliphatic hydrocarbons, such as chlorobenzenes,chloroethylenes or methylene chloride, aliphatic hydrocarbons, such ascyclohexane or paraffins, for example mineral oil fractions, alcohols,such as butanol or glycol as well as their ethers and esters, ketones,such as acetone, methyl ethyl ketone, methyl isobutyl ketone orcyclohexanone, strongly polar solvents, such as dimethylformamide anddimethylsulphoxide, as well as water. By liquefied gaseous extenders orcarriers are meant liquids which are gaseous at normal temperature andunder normal pressure, for example aerosol propellants, such ashalogenated hydrocarbons as well as butane, propane, nitrogen and carbondioxide. As solid carriers there are suitable: for example, groundnatural minerals, such as kaolins, clays, talc, chalk, quartz,attapulgite, montmorillonite or diatomaceous earth, and ground syntheticminerals, such as highly-dispersed silicic acid, alumina and silicates.As solid carriers for granules there are suitable: for example, crushedand fractionated natural rocks such as calcite, marble, pumice,sepiolite and dolomite, as well as synthetic granules of inorganic andorganic meals, and granules of organic material such as sawdust, coconutshells, corn cobs and tobacco stalks. As emulsifying and/or foam-formingagents there are suitable: for example, non-ionic and anionicemulsifiers, such as polyoxyethylene-fatty acid esters,polyoxyethylene-fatty alcohol ethers, for example alkylaryl polyglycolethers, alkylsulphonates, alkyl-sulphates, arylsulphonates as well asalbumin hydrolysis products. As dispersing agents there are suitable:for example, lignin-sulphite waste liquors and methylcellulose.

Adhesives such as carboxymethylcellulose and natural and syntheticpolymers in the form of powders, granules or latices, such as gumarabic, polyvinyl alcohol and polyvinyl acetate, as well as naturalphospholipids, such as cephalins and lecithins, and syntheticphospholipids, can be used in the formulations. Further additives can bemineral and vegetable oils.

It is possible to use colorants such as inorganic pigments, for exampleiron oxide, titanium oxide and Prussian Blue, and organic dyestuffs,such as alizarin dyestuffs, azo dyestuffs and metal phthalocyaninedyestuffs, and trace nutrients such as salts of iron, manganese, boron,copper, cobalt, molybdenum and zinc.

The formulations in general contain between 0.1 and 95 per cent byweight of active compound, preferably between 0.5 and 90%.

The active compounds according to the invention can be present in theformulations as a mixture with other known active compounds, such asfungicides, insecticides, acaricides and herbicides, and also asmixtures with fertilizers and other growth regulators.

The active compounds can be used as such, in the form of theirformulations or as the use forms prepared therefrom, such asready-to-use solutions, emulsifiable concentrates, emulsions, foams,suspensions, wettable powders, pastes, soluble powders, dusting agentsand granules. They are used in the customary manner, for example bywatering, spraying, atomizing, scattering, dusting, foaming, coating andthe like. Furthermore, it is possible to apply the active compounds inaccordance with the ultra-low volume process or to inject the activecompound preparation or the active compound itself into the soil. It isalso possible to treat the seeds of the plants.

When the compounds according to the invention are used as fungicides theamount applied can be varied within a substantial range depending uponthe type of application. Thus the active compound concentrations in theuse forms in the treatment of parts of plants are generally between 1and 0.0001% by weight, preferably between 0.5 and 0.001%. In thetreatment of seeds, in general amounts of active compounds of 0.001 to50 g for each kilogram of seed, preferably 0.01 to 10 g, are required.In the treatment of soil, active compound concentrations of 0.00001 to0.1% by weight, preferably 0.0001 to 0.02%, are necessary at the placeof action.

The preparation and the use of the compounds according to the inventioncan be seen from the following examples.

PREPARATION EXAMPLES Example 1 ##STR27##

A solution of 20.5 g (0.077 mol) of2-(4-chlorophenylethyl)-2-(1,1-dimethylbutyl)-oxirane, 5.3 g (0.077 mol)of 1,2,4-triazole, 1.0 g (0.025 mol) of sodium hydroxide, 1 ml of waterand a spatula tipful of α,α'-azoisobutyronitrile in 50 ml ofN-methylpyrrolidone is heated at 120° C. for 5 hours. After this, thesolution is cooled to room temperature and concentrated by stripping offthe solvent under reduced pressure, the remaining residue is dissolvedin acetic acid and washed three times with water, the organic phase isdried over sodium sulphate and the solvent is removed under reducedpressure. The residue is purified by column chromatography (silica gel;dichloromethane:ethyl acetate=4:1). In this manner 16.0 g (61.9% oftheory) of1-(4-chlorophenyl)-4,4-dimethyl-3-(1,2,4-triazol-1-yl-methyl)-3-heptanolare obtained in the form of a yellow oil.

Preparation of starting products ##STR28##

A solution of 18.2 g (0.106 mol) of m-chloroperbenzoic acid in 250 ml ofdichloromethane is added dropwise to a boiling solution of 22 g (0.88mol) of 2-(4-chlorophenylethyl)-3,3-dimethyl-1-hexene in 100 ml ofdichloromethane during the course of 2.5 hours. The mixture is heatedfor a further 2 hours under reflux, then cooled to room temperature,initially washed three times with 1N aqueous sodium hydroxide solutionand thereafter with water, and the organic phase is then dried oversodium sulphate and concentrated by stripping off the solvent underreduced pressure. 20.5 g of a colourless oil, which according to gaschromatographic and mass spectrometric analysis consists to 89.6% of2-(4-chlorophenylethyl)-2-(1,1-dimethylbutyl)-oxirane, are obtained.Accordingly, the yield is calculated as 78.5% of theory. The product isused for the further reaction without additional purification. ##STR29##

A suspension of 47.4 g (0.133 mol) of methyl-triphenylphosphoniumbromide and 15.3 g (0.137 mol) of potassium tert.-butylate in 250 ml ofabsolute toluene is heated under reflux for 30 minutes under drynitrogen. 25.3 g (0.1 mol) of1-(4-chlorophenyl)-4,4-dimethyl-3-heptanone, dissolved in 10 ml ofabsolute toluene, are then added dropwise during the course of 5minutes. The reaction mixture is heated under reflux for a further 15hours, then cooled to room temperature, washed twice with water andconcentrated under reduced pressure. The residue is taken up in ethylacetate, cooled to 5° C. and the crop of crystals formed is filtered offby suction. The filtrate is concentrated and distilled under reducedpressure. 23 g (91.8% of theory) of2-(4-chlorophenylethyl)-3,3-dimethyl-1-hexene are obtained in the formof a yellow oil of boiling point 85°-87° C./0.1 mbar. ##STR30##

15 g of Raney nickel are added to a solution of 92 g (0.37 mol) of1-(4-chlorophenyl)-4,4-dimethyl-1,6-heptadien-3-one in 400 ml oftetrahydrofuran and the mixture is stirred for 2.5 hours at 40° C. undera hydrogen pressure of 50 bar in an autoclave. After this, the reactionmixture is filtered and concentrated under reduced pressure. Afterdistillation of the residue in vacuo, 55 g (58.9% of theory) of1-(4-chlorophenyl)-4,4-dimethyl-3-heptanone are obtained in the form ofa yellow oil of boiling point 179° C./16 mbar. ##STR31##

40 ml of water are added to a solution of 56.2 g (0.4 mol) of4-chlorobenzaldehyde and 50.4 g (0.4 mol) of 4,4-dimethyl-1-hexen-5-onein 200 ml of ethanol and directly thereafter a solution of 1.2 g ofsodium hydroxide in 12 ml of water is added. The mixture is initiallystirred for 1 hour at room temperature, then 0.8 g of solid sodiumhydroxide is added and the mixture is stirred for a further 16 hours. Itis then diluted with water and extracted with ethyl acetate. The ethylacetate extract is washed three times with water, dried andconcentrated. 92 g (92.5% of theory) of1-(4-chlorophenyl)-4,4-dimethyl-1,6-heptadien-3-one are obtained in theform of a yellow oil. ##STR32##

A mixture of 121 g (1.0 mol) of 3-bromopropene and 103 g (1.2 mol) of3-methyl-2-butanone is added dropwise during the course of 2 hours to asuspension of 168 g (3.0 mol) of potassium hydroxide powder and 10 g oftetrabutylammonium bromide in 300 ml of toluene with stirring. Duringthis addition, the reaction temperature is kept below 30° C. Thereaction mixture is kept at room temperature for a further 2 hours, thenmixed with water, and the organic phase is separated. The organic phaseis washed twice with water, dried and distilled through a packed columnat ambient pressure. 40 g (31.7% of theory) of4,4-dimethyl-1-hexen-5-one are obtained as a clear liquid of boilingpoint 151°-154° C.

Example 2 ##STR33##

A solution of 89 g (0.352 mol) of2-(4-chlorophenylethyl)-2-pentyl-oxirane, 26.5 g (0.384 mol) of1,2,4-triazole, 3.5 g (0.0875 mol) of sodium hydroxide, 1.2 ml of waterand a spatula tipful of α,α'-azoisobutyronitrile in 175 ml ofN-methylpyrrolidone is heated at 120° C. for 4 hours. After this themixture is cooled to room temperature and concentrated by stripping offthe solvent under reduced pressure, the remaining residue is dissolvedin ethyl acetate and washed three times with water, the organic phase isdried over sodium sulphate and the solvent is removed under reducedpressure. The residue is purified by column chromatography (silica gel;dichloromethane:ethyl acetate=1:1). In this manner 53.2 g (47.0% oftheory) of 1-(4-chlorophenyl)-3-(1,2,4-triazol-1-yl-methyl)-3-octanolare obtained in the form of a yellow oil.

Preparation of starting products ##STR34##

38 ml (0.61 mol) of iodomethane are added dropwise to a cooled solutionof 47.6 ml (0.65 mol) of dimethyl sulphide in 280 ml of absolutedimethyl sulphoxide and 150 ml of absolute tetrahydrofuran. The mixtureis stirred at room temperature for 16 hours. A solution of 97.5 g (0.41mol) of 1-(4-chlorophenyl)-3-octanone in 400 ml of absolute toluene isadded, the reaction mixture is cooled to 0°-5° C. and 41 g (0.76 mol) ofsodium methylate are added in portions in the course of 3 hours. Themixture is stirred for a further 15 hours at room temperature, then 1 lof water is added, the organic phase is separated off and the aqueousphase is extracted once with toluene. The combined organic phases arewashed twice with plenty of water, dried over sodium sulphate andconcentrated by stripping off the solvent under reduced pressure. 93.2 gof a colorless oil which, according to gas chromatographic and massspectrometric analysis consists to 84.5% of2-(4-chlorophenylethyl)-2-pentyloxirane, are obtained. Accordingly, theyield is calculated as 76.1% of theory. The product is used for thefurther reaction without additional purification. ##STR35##

15 g of Raney nickel are added to a solution of 100 g (0.423 mol) of1-(4-chlorophenyl)-1-octen-3-one in 500 ml of toluene and the mixture isstirred for 5 hours at 60° C. under a hydrogen pressure of 70-90 bar inan autoclave. After this the reaction mixture is filtered andconcentrated under reduced pressure. 97.3 g (96.4% of theory) of1-(4-chlorophenyl)-3-octanone are obtained in the form of a colorlessoil. ##STR36##

70 ml of water are added to a solution of 90 g (0.64 mol) of4-chlorobenzaldehyde and 68.5 g (0.6 mol) of 2-heptanone in 300 ml ofethanol and directly thereafter a solution of 1.7 g of sodium hydroxidein 17 ml of water is added. The mixture is initially stirred for 1 hourat room temperature, then 0.6 g of solid sodium hydroxide is added andthe mixture is stirred for a further 64 hours. The precipitated productis filtered off with suction, washed with 1 liter of water, pressed outon a clay plate and then dried in vacuo for 16 hours over phosphoruspentoxide. 135 g (95.1% of theory) of 1-(4-chlorophenyl)-1-octen-3-oneare obtained in the form of a pale yellow solid of melting point 44°-47°C.

The compounds shown in the following table by formula are also preparedaccording to the method given in Example 2.

                                      TABLE                                       __________________________________________________________________________     ##STR37##                                                                         Compound                                                                 Example                                                                            No.   Z.sub.m R            Characterization by                           __________________________________________________________________________    3    (I-3) 4-Cl    (CH.sub.2).sub.5CH.sub.3                                                                   NMR spectrum                                  4    (I-4) 4-Cl    (CH.sub.2).sub.6CH.sub.3                                                                   NMR spectrum                                  5    (I-5) 4-Cl    CH.sub.2CH.sub.2CH(CH.sub.3).sub.2                                                         Melting point                                                                 78-79° C.                              6    (I-6) 4-CHNOCH.sub.3                                                                        CH.sub.2CH(CH.sub.3).sub.2                                                                 NMR spectrum                                  7    (I-7) 4-CHNOCH.sub.3                                                                        CH.sub.2CH.sub.2CH(CH.sub.3).sub.2                                                         NMR spectrum                                  8    (I-8) 4-Cl    CH.sub.2CH(CH.sub.3).sub.2                                                                 NMR spectrum                                  9    (I-9) 4-Cl                                                                                   ##STR38##   Melting point 112-113° C.              10   I-10  4-F                                                                                    ##STR39##   Melting point 52-55° C.                11   I-11  4-F                                                                                    ##STR40##   Melting point 83-84° C.                12   I-12  --                                                                                     ##STR41##   Melting point 84,5° C.                 13   I-13  4-OCF.sub.3                                                                            ##STR42##   NMR spectrum                                  14   I-14  4-CH.sub.3                                                                             ##STR43##   NMR spectrum                                  __________________________________________________________________________

FIG. 1 represents the nuclear magnetic resonance spectrum characteristicof the compound prepared in Example 1.

FIG. 2 represents the nuclear magnetic resonance spectrum characteristicof the compound prepared in Example 2.

FIG. 3 represents the nuclear magnetic resonance spectrum characteristicof the compound prepared in Example 3.

FIG. 4 represents the nuclear magnetic resonance spectrum characteristicof the compound prepared in Example 4.

FIG. 5 represents the nuclear magnetic resonance spectrum characteristicof the compound prepared in Example 6.

FIG. 6 represents the nuclear magnetic resonance spectrum characteristicof the compound prepared in Example 7.

FIG. 7 represents the nuclear magnetic resonance spectrum characteristicof the compound prepared in Example 8.

FIG. 8 represents the nuclear magnetic resonance spectrum characteristicof the compound prepared in Example 13.

FIG. 9 represents the nuclear magnetic resonance spectrum characteristicof the compound prepared in Example 14.

The compound given below is employed as a comparison substance in thefollowing use examples: ##STR44##

EXAMPLE A Venturia test (apple)/curative

Solvent: 4.7 parts by weight of acetone

Emulsifier: 0.3 parts by weight of alkylaryl polyglycol ether

To produce a suitable preparation of active compound, 1 part by weightof active compound is mixed with the stated amounts of solvent andemulsifier, and the concentrate is diluted with water to the desiredconcentration.

To test for curative activity, young plants are inoculated with anaqueous conidia suspension of the apple scab causative organism(Venturia inaequalis). The plants remain in an incubation cabin at 20°C. and 100% relative atmospheric humidity for 1 day and are then placedin a greenhouse. After a given number of hours, the plants are sprayedwith the preparation of active compound until dripping wet.

The plants are then placed in a greenhouse at 20° C. and a relativeatmospheric humidity of about 70%.

Evaluation is carried out 12 days after the inoculation.

The substances (I-1) and (I-7) according to the invention exhibit abetter action than the comparative substance (A) in this test.

EXAMPLE B Cercospora test (mungo bean)/protective

Solvent: 4.7 parts by weight of acetone

Emulsifier: 0.3 parts by weight of alkyl-aryl polyglycol ether

To produce a suitable preparation of active compound, 1 part by weightof active compound is mixed with the stated amounts of solvent andemulsifier, and the concentrate is diluted with water to the desiredconcentration.

To test for protective activity, young plants are sprayed with thepreparation of active compound until dripping wet. After the spraycoating has dried, the plants are inoculated with an aqueous sporesuspension of Cercospora canescens and remain in a dark incubation cabinat 22° C. and 100% relative atmospheric humidity for one day.

The plants are placed in an illuminated greenhouse at about 23° C. and arelative atmospheric humidity of about 80%.

Evaluation is carried out 20 days after the inoculation.

The substances (I-7) and (I-8) according to the invention exhibit abetter activity than the comparative substance (A) in this test.

EXAMPLE C Plant tolerance test

Test plant: cucumber

Duration of the test: 7 days

Solvent: 4.7 parts by weight of acetone

Emulsifier: 0.3 part by weight of alkyl-aryl polyglycol ether

To produce a suitable preparation of active compound, 1 part by weightof active compound is mixed with the stated amounts of solvent andemulsifier, and the concentrate is diluted with water to the desiredconcentration.

Young plants are sprayed with this preparation of active compound untildripping wet and are placed in a greenhouse at about 20° C.

The plants are evaluated for damage, such as impairment of growth,discoloration and necrosis.

The compounds (I-1) and (I-7) according to the invention exhibit abetter tolerance than the comparative substance (A) in this test.

EXAMPLE D Erysiphe test (barley)/seed treatment

The active compounds are used as dry dressings. These are prepared byextending the particular active compound with a ground mineral to give afinely pulverulent mixture, which ensures uniform distribution on theseed surface.

To apply the dressing, the seed is shaken with the dressing in a closedglass flask for 3 minutes.

3 batches of 12 grains of the barley are sown 2 cm deep in standardsoil. 7 days after sowing, when the young plants have unfolded theirfirst leaf, they are dusted with spores of Erysiphe graminis f. sp.hordei.

The plants are placed in a greenhouse at a temperature of about 20° C.and a relative atmospheric humidity of about 80% in order to promote thedevelopment of mildew pustules.

Evaluation is carried out 7 days after the inoculation.

The compound (I-8) according to the invention exhibits a better actionthan the comparative substance (A) in this test.

It is understood that the specification and examples are illustrativebut not limitative of the present invention and that other embodimentswithin the spirit and scope of the invention will suggest themselves tothose skilled in the art.

We claim:
 1. An oxirane of the formula ##STR45## in which R represents aradical of the formula --CH₂ --CH(CH₃)₂, --(CH₂)₄ --CH₃, --(CH₂)₅ --CH₃,--(CH₂)₆ --CH₃, ##STR46## Z represents fluorine, chlorine, methyl,trifluoromethoxy or methoximinomethyl, andm represents 0 or
 1. 2. Acompound according to claim 1, wherein such compound is2-(4-chloro-phenylethyl)-2-(1,1-dimethylbutyl)-oxirane of the formula##STR47##